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J. Am. Chem. Soc. 2000, 122, 1314-1324

First Stepwise Do¨tz Reaction: Isolation and Characterization of a Chelated Metallatriene Intermediate. Influence of Its Pattern of Substitution in Product Partition Jose´ Barluenga,*,† Fernando Aznar,† Ignacio Gutie´ rrez,† Alfredo Martı´n,†,§ Santiago Garcı´a-Granda,‡ and M. Amparo Llorca-Baragan˜ o‡ Contribution from the Instituto UniVersitario de Quı´mica Organometa´ lica “Enrique Moles”, Unidad asociada al C.S.I.C., Julia´ n ClaVerı´a 8, E-33701 OViedo, Spain, and Departamento de Quı´mica Fı´sica y Analı´tica (X-ray serVice), UniVersidad de OViedo, Julia´ n ClaVerı´a 8, E-33701 OViedo, Spain ReceiVed June 4, 1999

Abstract: A series of chelated tetracarbonyl aminovinyl carbene complexes 5 are prepared by high-yielding decarbonylation reaction. γ-Alkyl-substituted complexes 5a-d are stable in solid form while γ-aryl-substituted analogues 5e-g are stable only in solution. NMR studies determined that complexes 5 undergo a dynamic process in solution, in which the unsaturated η1 species are present in low concentration. Reaction of complexes 5 with electron-deficient alkynes under controlled conditions afforded the 1,4,5-η3-dienylcarbene complexes 9 arising from the insertion of the alkyne in the metal-carbon bond. The stability and behavior of these complexes were studied and found to be related to their electronic structure and pattern of substitution. Thermal decomposition of carbenes 9 produced either cyclopentadienes 13 or phenol derivatives 15, the major products in the Do¨tz reaction, thus demonstrating that they can be the actual intermediates in this reaction. The overall process can be considered a Do¨tz reaction carried out in three separate steps at low temperature.

Introduction Despite the synthetic value of the benzannulation reaction of Fischer carbene complexes and alkynes,1 the details of its mechanism remain to be ascertained.2 Great efforts are being made to establish the role of each proposed intermediate in the outcome of the reaction. In particular, knowledge of the effect of the structure and stereoelectronic properties of the intermediates in the product distribution would improve significantly the ability to tune the reaction to a particular final product. The widely accepted mechanism for the reaction is depicted in Scheme 1. The process is initiated by the dissociation of a CO ligand from complex I to produce the coordinatively unsaturated carbene complex II.3 Intermediate II is trapped by * To whom correspondence should be addressed. E-mail: Barluenga@ sauron.quimica.uniovi.es. Fax: (+) 34 8 510 34 50. † Instituto Universitario de Quı´mica Organometa ´ lica “Enrique Moles”. ‡ Universidad de Oviedo. § New address: Lilly, S.A., Avda de la Industria, 30, 28108-Alcobendas, Madrid. (1) For reviews on the synthetic applications of Fischer carbene complexes, see: (a) Do¨tz, K. H. Angew. Chem., Int. Ed. Engl. 1984, 23, 587. (b) Wulff, W. D. In ComprehensiVe Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 469-547. (c) Hegedus, L. S. In ComprehensiVe Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 549-576. (d) Doyle, M. In ComprehensiVe Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 387-420. (e) Harvey, D. F.; Sigano. D. M. Chem. ReV. 1996, 96, 271. (2) For discussions of, and recent citations to mechanistic issues, see: (a) Waters, M. L.; Brandvold, T. A.; Isaacs, L.; Wulff, W. D.; Rheingold, A. L. Organometallics 1998, 17, 4298. (b) Hsung, R. P.; Quinn, J. F.; Weisemberg, B. A.; Wulff, W. D.; Yap, G. P. A.; Rheingold, A. L. Chem. Commun. 1997, 615. (c) Gross, M. F.; Finn, M. G. J. Am. Chem. Soc. 1994, 116, 10921. (d) Wulff, W. D.; Bax, B. M.; Brandvold, T. A.; Chan, K. S.; Gilbert, A. M.; Hsung, R. P.; Mitchell, J.; Clardy, J. Organometallics 1994, 13, 102. (e) Bos, M. E.; Wulff, W. D.; Miller, R. A.; Chamberlin, S.; Brandvold, T. A. J. Am. Chem. Soc. 1991, 113, 9293. (3) Fischer, H.; Mu¨hlemeier, J.; Ma¨rkl, R.; Do¨tz, K. H. Chem. Ber. 1982, 115, 1355.

Scheme 1

the alkyne present in the medium, which binds the metal in such a way that the bulkier substituent RL is placed parallel to the trans CO to avoid unfavorable steric interactions with the

10.1021/ja991865j CCC: $19.00 © 2000 American Chemical Society Published on Web 02/03/2000

First Stepwise Do¨ tz Reaction

J. Am. Chem. Soc., Vol. 122, No. 7, 2000 1315

Scheme 2

carbene ligand in complex III.4 This coordination geometry will be ultimately responsible for the regiochemistry observed in the final products. The next step is the insertion of the alkyne into the metal-carbon double bond to afford metallatrienes IV. This step can lead to two different isomers of the η3-metallatrienes, of which only the E isomer should be able to undergo cyclization with the terminal double bond, giving rise to the cyclopentadiene (indene) VIII and phenol (naphthol) IX.5 On the other hand, the Z derivative is the one responsible for the formation of furan X.6 Isolating the intermediates and studying their structure and submission to the next mechanistic step in a reaction are, theoretically, the best means of understanding them. However, since the CO dissociation step in the benzannulation reaction is rate limiting, the detection of subsequent intermediates has been cumbersome. Thus, only cleverly designed stereochemically or functionally restricted analogues have been isolated and used to estimate the structural characteristics of the actual intermediates.7-10 To the best of our knowledge, only one intermediate capable of undergoing the subsequent step has been isolated and characterized, namely the last one, the metalcomplexed cyclohexadienone VII.2d As stated above, the stereoelectronic properties of the intermediates, especially of those situated in the branching of the reaction pathway, are crucial for the product partition. Unfortunately, little is known about these intermediates. Theoretical calculations on models for several of the intermediates have shed some light on the energetics of the mechanism.11-13 Also, rigorous evaluation of the proportions of the final products (including minor ones) and correlation with the electronic and steric properties of the starting materials have allowed us to infer the properties of the intermediates.2d,e Despite this, there are still some unanswered questions, especially concerning the reaction of alkenylcarbene complexes. (4) (a) Do¨tz, K. H.; Dietz, R. Chem. Ber. 1978, 111, 2517. (b) Do¨tz, K. H.; Pruskil, I. Chem. Ber. 1980, 113, 2876. (c) Wulff, W. D.; Tang, P. C.; McCallum, J. S. J. Am. Chem. Soc. 1981, 103, 7677. (d) Do¨tz, K. H.; Mu¨hlemeier, J.; Schubert, U.; Orama, O. J. Organomet. Chem. 1983, 247, 187. (e) Wulff, W. D.; Chang, K. S.; Tang, P. C. J. Org. Chem. 1984, 49, 2293. (f) Yamashita, A.; Toy, A. Tetrahedron Lett. 1986, 27, 3471. (5) It has also been proposed for the formation of phenol (naphthol) IX a manifold involving CO insertion in complex V followed by reductive elimination and tautomerization: Casey, C. P. In ReactiVe Intermediates; Jones, M., Jr., Moss, R. A., Eds.; Wiley: New York, 1981; Vol. 2, p 155. (6) McCallum, J. S.; Kunng, F. A.; Gilbertson, S. R.; Wulff, W. D. Organometallics 1988, 7, 2346. (7) (a) Do¨tz, K. H.; Scha¨fer, T.; Kroll, F.; Harms, K. Angew. Chem., Int. Ed. Engl. 1992, 31, 1236. (b) Hohmann, F.; Siemoneit, S.; Nieger, M.; Kotila, S.; Do¨tz, K. H. Chem. Eur. J. 1997, 3, 853. (8) Do¨tz, K. H. Angew. Chem., Int. Ed. Engl. 1979, 18, 954. (9) (a) Anderson, B. A.; Wulff, W. D.; Rheingold, A. L. J. Am. Chem. Soc. 1990, 112, 8615. (b) Chelain, E.; Goumont, R.; Hamon, L.; Parlier, A.; Rudler, M.; Rudler, H.; Daran, J. C.; Vaissermann, J. J. Am. Chem. Soc. 1992, 114, 8088. (10) Tang, P. C.; Wulff, W. D. J. Am. Chem. Soc. 1984, 106, 1132. (11) Gleichmann, M. M.; Do¨tz, K. H.; Hess, B. A. J. Am. Chem. Soc. 1996, 118, 10551. (12) (a) Hoffmann, P.; Ha¨mmerle, M. Angew. Chem., Int. Ed. Engl. 1989, 28, 908. (b) Hoffmann, P.; Ha¨mmerle, M. Unfried, G. New J. Chem. 1991, 15, 769. (13) (a) Torrent, M.; Duran, M.; Sola´, M. Organometallics 1998, 17, 1492. (b) Torrent, M.; Duran, M.; Sola´, M. Chem. Commun. 1998, 999. (c) Torrent, M.; Duran, M.; Sola´, M. J. Am. Chem. Soc. 1999, 121, 1309.

Table 1. Pentacarbonyl Aminovinyl Carbene Complexes Prepared compd 1a 1b 1c 1d 1e 1f 1g 1h 1i a

R1

R2

CH2CH2CH2 O(CH2)2CH2 CH3 H CH3 CH2OCH3 H Ph H 2-furyl H 2-furyl H 2-furyl H 2-furyl

R3

R4

CH2CH2OCH2CH2 CH2CH2OCH2CH2 CH2CH2OCH2CH2 CH2CH2OCH2CH2 CH2CH2OCH2CH2 CH2CH2OCH2CH2 Me Me Me H H H

method

yield (%)

metathesis metathesis metathesis metathesis aminolysis aminolysis aminolysis aminolysis aminolysis

69a 41 55 75 99 99 99 99 99

See ref 17.

For instance, there is no clear reason why reactions of arylcarbene complexes with alkynes give so many different products and are so sensitive to changes in solvents and concentration while reactions of alkenyl carbenes only give sixmembered rings with very few side products and are almost unaffected by changes in reaction conditions.2d Also, the electronic effects that have been proposed to explain the exclusive formation of indene derivatives for arylamino carbenes do not seem to work in the case of alkenylamino carbenes, since the reactions of this type of carbenes with alkynes give mainly aminophenols instead of aminocyclopentadienes.14 In the present contribution we report the first example of a stepwise Do¨tz reaction, in which the decarbonylation step is carried out in the absence of alkyne. This has permitted us to isolate complexes analogous to II. We describe the insertion of alkynes in these compounds at low temperature, which led to the isolation and characterization of the metallatriene intermediates of the Do¨tz reaction IV. Finally, we study the thermal evolution of these intermediates and the effect of their pattern of substitution in the distribution between cyclopentadiene and the phenol derivatives.15 Results Aminocarbenes 1 (Scheme 2, Table 1) were prepared by two standard methods. Aminolysis of alkoxycarbenes 2 was performed on β-aryl-substituted complexes, giving rise to the aminocarbene derivatives in almost quantitative yields. However, in the reaction of the alkyl analogues with amines, variable amounts of complexes (CO)5(R2NH)Cr are formed as side products, depending on the substituents of the amine and the carbene complex.16 Therefore, complexes 1, bearing an alkyl or hydrogen substituent in the β-position were synthesized by metathesis of 2-aminodienes 3 and pentacarbonylmethoxy(phenyl)carbene chromium 4.17 In some cases, variable amounts (14) (a) Wulff, W. D.; Gilbert, A. M.; Hsung, R. P.; Rahm, A J. Org. Chem. 1995, 60, 4566. (b) Barluenga, J.; Lo´pez, L. A.; Martı´nez, S.; Toma´s, M. J. Org. Chem. 1998, 63, 7588. (15) A preliminary account of this report has been published: Barluenga, J.; Aznar, F.; Martı´n, A.; Garcı´a-Granda, S.; Pe´rez-Carren˜o, E. J. Am. Chem. Soc. 1994, 116, 11191. (16) This behavior has been previously reported: (a) Anderson, B. A.; Wulff, W. D.; Powers, T. S.; Tribbitt, S.; Rheingold, A. L. J. Am. Chem. Soc. 1992, 114, 10784. (b) Fischer, E. O.; Heckl, B.; Werner, H. J. Organomet. Chem. 1971, 28, 359. (c) Chelain, E.; Goumont, R.; Hamon, L.; Parlier, A.; Rudler, M.; Rudler, H.; Daran, J.-C.; Vaissermann, J. J. Am. Chem. Soc. 1992, 114, 8088. (17) Barluenga, J.; Aznar, F.; Martı´n, A. Organometallics 1995, 14, 1429.

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Barluenga et al.

Scheme 3

Table 2. Complexes 5 Prepared compd 5a 5b 5c 5d a

R1

CH3 CH3

R2 CH2CH2CH2 O(CH2)2CH2 H CH2OCH3

yielda (%) 94 (90) 84 90 (77) 88 (80)

Yields given in parentheses correspond to the thermal reaction.

of tetracarbonyl carbene complexes 5 (Scheme 3) are formed as side products in the metathesis reaction, but these compounds can be transformed quantitatively into their pentacarbonyl analogues 1 by simply bubbling CO through the crude reaction solutions. This fact suggested that the tetracarbonyl complexes 5 could be formed from 1 under thermal conditions. Complexes 5a, 5c, and 5d (Scheme 3, Table 2) were prepared by heating solutions of the pure pentacarbonyl complexes 1 in THF (complex 5a) or toluene (complexes 5c and 5d) at reflux temperature. However, to avoid the long periods of time required to complete the reaction, that lead to partial decomposition of the starting and final complexes, we tried to carry out this reaction photochemically. Thus, when irradiated at -40 °C, a carbonyl ligand dissociates from the aminovinyl carbene complex to afford the stable tetracarbonyl species 5.18 The best conditions found for this transformation were the irradiation of a THF solution of the carbene complex in a Pyrex Schlenk tube at -40 °C while a constant flow of N2 was bubbled through the reaction in order to remove the released CO. Complexes 5a-d are stable in solid form under inert atmosphere and can be stored at -20 °C for several months. The structure of complexes 5 was postulated on the basis of their NMR spectra. Especially relevant are their signals corresponding to the double bond, which are shielded as a consequence of the metal complexation (δ ) 85.7 for the CH and 86.9 for the quaternary carbon of complex 5a). The X-ray structure17 of complex 5a shows clearly the interaction of the double bond with the metal in a fashion similar to that reported previously for η3-vinyl carbenes (η3-allylidenes).19 As far as we know, no examples of η3-vinyl carbenes have been reported in the literature for d6 group VI metals.20 The behavior of 1e-g with respect to CO dissociation is similar to that of 1a-d. Irradiation of their THF solutions at -40 °C produced the corresponding tetracarbonyl complexes 5e-g. However, the isolation of complexes 5e-g was elusive due to product decomposition in the solid form. To ascertain the formation of complexes 5e-g, a solution of 1e in CD2Cl2 was irradiated at -40 °C under static vacuum. The NMR analysis of this sample showed signals assignable to 5e along with those corresponding to the starting material. Thus, com(18) The main photoprocess of Fischer carbene complexes is the decarbonylation: (a) Foley, H. C.; Strubinger, L. M.; Targos, T. S.; Geoffrey, G. L. J. Am. Chem. Soc. 1983, 105, 3064. (b) Bell, S. E. J.; Gordon, K. C.; McGarvey, J. J. J. Am. Chem. Soc. 1988, 110, 3107. (c) Knorr, J. R.; Brown, F. L. Organometallics 1994, 13, 2178. (19) Garret, K. E.; Sheridan, J. B.; Pourreau, D. B.; Feng, W. C.; Geoffrey, G. L.; Staley, D. L.; Rheingold, A. L. J. Am. Chem. Soc. 1989, 111, 8383. (20) For leading references on η3-vinyl carbenes, see: Mitsudo, T. Bull. Chem. Soc. Jpn. 1998, 71, 1525.

pounds 5e-g were generated and used in subsequent reactions without isolation. Irradiation of complexes 1h and 1i bearing one or two N-H bonds, respectively, did not provide the expected tetracarbonyl η3-vinyl carbene derivatives. This behavior contrasts with that described for the N,N-dialkyl derivatives and must be ascribed to the presence of the N-H bonds, since this is the only difference in the structures of 1h and 1i.21 Complexes 5 are, in solution, in equilibrium between the chelated (η3-vinyl carbene ligand) and nonchelated (η1-vinyl carbene ligand) forms, probably due to the strain created by the small chelation ring. This behavior was inferred from the NMR analysis of complexes 5. For example, complex 5c shows no signals in the metal-complexed carbonyl region. If the temperature is raised to 50 °C, a single signal appears at 231.1 ppm. On the other hand, the spectrum at -20 °C showed three signals in the carbonyl region at 224.4, 227.1, and 237.3 (double intensity22) ppm. This type of behavior has been described before for chelated tetracarbonyl (acylamino)carbene23 and trialkylsilyl aminocarbene24 complexes, but, to the best of our knowledge, it has never been observed before for a C-C double bond chelated Fischer carbene complex. Interestingly, the signals corresponding to the rest of the carbons of the complex remain almost invariable throughout the temperature range. Especially indicative are the signals for the C-C double bond which remain within a range of 1 ppm of 82.5 (CH) and 57.4 (CH2) ppm. This observation indicates that an equilibrium between the η3-vinyl carbene (5) and the η1-vinyl carbene (5′) complexes occurs (Scheme 4). This η1-vinyl carbene complex 5′ is Scheme 4

pentacoordinated and probably fluxional.25 A fast interchange of the four carbonyl ligands occurs before the η1 complex reverts to the η3 isomer. Since no signals assignable to a nonchelated carbene appear, the population of the η1 complex 5′ must be necessarily low. This fact implies that the η3-vinyl carbene is not only more stable than the η1 isomer but also more stable than its solvent (THF)-complexed analogue 5‚S, which is, in principle, readily accessible from it. The ready availability of the unsaturated species 5′ at room temperature prompted us to investigate the participation of isolated complexes 5 in the Do¨tz reaction. To prove that tetracarbonyl complexes 5 are true intermediates, we tested the reaction of 5a with a series of alkynes. The reaction gave unsatisfactory results in most cases when electron-rich or normal (21) The decarbonylation reaction was also tried with some alkoxyvinyl carbenes, but we found them inert to either photochemical or thermal conditions. Theorethical calculations anticipated the lower stabilization gained by chelation of the vinyl group in alkoxyvinyl carbenes, as compared with the aminovinyl carbenes.11 (22) The fact that the two cis carbonyl ligand 13C NMR chemical shifts are identical is fortuitous, since both carbon atoms have different environments due to the substituents in the double bond. For example, these carbon atoms have different chemical shifts in complex 5a (see Experimental Section). (23) Grotjahn, D. B.; Do¨tz, K. H. Synlett 1991, 381. (24) Hepp, W.; Schubert, U. J. Organomet. Chem. 1990, 385, 221. (25) Hofmann, P.; Ha¨mmerle, M. Angew. Chem., Int. Ed. Engl. 1989, 28, 908.

First Stepwise Do¨ tz Reaction alkynes were employed. Thus, although tetracarbonyl carbene complexes 5 are stable at room temperature in a solution of THF for long periods of time, they react readily with an added acetylene such as phenylacetylene to produce the pentacarbonyl complex 1a as the only identifiable product, in 46% yield (Scheme 5). When the reaction is carried out at THF reflux Scheme 5

J. Am. Chem. Soc., Vol. 122, No. 7, 2000 1317 Table 3. Complexes 9 Prepared compd 9a 9b 9c 9d 9e 9f 9g 9h 9i 9j 9k 9l

R1

R2

CH2CH2CH2 OCH2CH2CH2 CH3 H CH3 CH2OCH3 H Ph H 2-furyl H 2-furyl H 2-furyl H 2-furyl H Ph H Ph H Ph

R3

R4

CH2CH2OCH2CH2 CH2CH2OCH2CH2 CH2CH2OCH2CH2 CH2CH2OCH2CH2 CH2CH2OCH2CH2 CH2CH2OCH2CH2 Me Me Me H H H CH2CH2OCH2CH2 CH2CH2OCH2CH2 CH2CH2OCH2CH2

R5

Z

yield (%)

CO2Me CO2Me CO2Me CO2Me CO2Me CO2Me CO2Me CO2Me CO2Me H H H

CO2Me CO2Me CO2Me CO2Me CO2Me CO2Me CO2Me CO2Me CO2Me CO2Me CONMe2 CN

54 95 73 69 55a 50a 35a 10a,b 9a,c 48a 54a 22a

a Yield based on complex 1. b With 55% recovery of 1h. c With 80% recovery of 1i.

temperature with an excess of alkyne, it is possible to isolate 6 and 7 as a 1:1 mixture in a global yield of 40%. In addition, a mass balance in the crude reaction indicated that 4-5 equiv of alkyne was consumed. On the other hand, when the reaction is performed with the pentacarbonyl complex 1a instead of the tetracarbonyl derivative 5a, it gives rise to the same mixture of products with 80% global yield. The products isolated in the reaction of phenylacetylene with tetracarbonyl complex 5a arise from the decomposition of this carbene to furnish the pentacarbonyl complex 1a in ca. 50%, which further reacts with phenylacetylene to give the same products but in lower yield. A possible interpretation of these results can be as follows: from the reaction of tetracarbonyl carbene with alkyne a tetracarbonyl species A arises that is susceptible of releasing 1 equiv of CO in the presence of a high concentration of a CO acceptor (5a). From this CO interchange would result 1 equiv of the pentacarbonyl complex 1a and 1 equiv of a tricarbonyl species capable of polymerizing the alkyne. When all the tetracarbonyl carbene 5a has been consumed, the normal Do¨tz process takes place from 1a. Tetracarbonyl complex 5a is regenerated from 1a, as well as the complex A arising from its reaction with phenylacetylene. Now the concentration of both intermediates is so low that the CO interchange process is difficult to achieve, and then the complex A evolves into the usual Do¨tz products. Fortunately, reaction of complexes 5 with electron-deficient alkynes was more fruitful. When carbene complex 5a (Scheme 6, Table 3) was treated with dimethyl acetylenedicarboxylate Scheme 6

(8) in CD2Cl2 at -80 °C, and the reaction mixture was allowed to warm slowly while being monitored by 13C NMR analysis, no change in the composition of the mixture was observed until -20 °C. At this temperature the appearance of a new set of signals could be observed corresponding to complex 9a, along with those of the pentacarbonyl carbene 1a, which comes from the aforementioned decomposition of 5a. The total disappear-

ance of the starting materials lasted 22 h, and during this time, no other signals assignable to any intermediate could be observed. At this temperature, complex 9a is stable, and no decomposition products were observed after 1 week. The structure of the observed complex 9a was deduced from its 13C NMR analysis, the most significant data being the following. The carbene carbon chemical shift is 245.9 ppm; 10 ppm upfield from that of 5a, 257.6 ppm. It is known that chemical shifts of carbene atoms correlate well with the electrondonating ability of their substituents; therefore, these high-field chemical shifts contrast with the fact that two electronwithdrawing ester groups are placed in the dienyl system of the complexes. The chemical shifts for two of the carbons belonging to the diene moiety are in the range of a noncoordinated C-C double bond (157.9 and 130.7 ppm) while the other two signals are displaced to high field (93.8 and 102.1 ppm), indicating that this double bond is coordinated to the metal. 13C-DEPT pulse sequence experiments showed that the terminal double bond is the one actually bonded to the metal. Finally, four signals assignable to the carbonyl carbons are observed at room temperature in the expected chemical shift range, indicative that chelate ring opening, if it happens, is slow in the NMR time scale. This is what could be expected, since ring strain in 9a is significantly lower than in complexes 5. To test the generality of the insertion process, carbene complexes 5a-g were reacted with a series of electron deficient alkynes to yield the complexes 9 (Scheme 6, Table 3) as solids after suitable workup (see Experimental Section). In these reactions, a variable amount of complexes 1 (up to 15%) is always recovered. Although in all cases the reaction was carried out at -20 °C, the procedure was dependent on the stability of the starting carbene complexes 5. Thus, in the case of complexes 9a-d, the starting materials were the corresponding previously isolated complexes 5a-d. On the other hand, since complexes 5e-g could not be isolated (vide supra), the reactions of these complexes were performed in one pot with the crude solutions after the photochemical CO dissociation of carbenes 1e-g. Finally, complexes 9h-i bearing at least one hydrogen at the nitrogen could be prepared by irradiation in situ of a 1:1 mixture of carbenes 1h-i and DMAD under carefully controlled conditions. The thermal stability of complexes 9 is surprisingly high, taking into account that the carbene carbon is directly attached to an electron-withdrawing group, and must be ascribed to an effective electron donation from the vinylogous amine. In fact, the rotation of the amine about the N-C bond is slow at room temperature, as can be deduced from the inequivalence of the carbons of the amine in 13C NMR. This stability is also

1318 J. Am. Chem. Soc., Vol. 122, No. 7, 2000

Barluenga et al.

dependent on the substitution pattern at the metallatriene complex. Thus, complexes 9a-d, in which R2 is an alkyl group or hydrogen and R5 is an ester (Scheme 6), evolve to the cyclopentannulation products overnight in solution at room temperature while complexes 9e-i (R2 ) Ar, R5 ) CO2Me) are stable for days in these conditions. On the other hand, carbenes arising from propiolic acid derivatives 9j-l (R5 ) H; Scheme 6) are also less stable than their DMAD analogue 9e, and, among them, the stability decreases as the electronwithdrawing capability of the group directly attached to carbene carbon increases. Finally, the unstability of the carbenes 9 reaches its maximum degree when both R5 and R2 are hydrogen. Thus, the reaction of the alkyl-substituted carbene 5c with methyl propiolate 10 led to a carbene complex that evolves to the Cr(CO)3 complexed phenol 11 (Scheme 7) at the reaction temperature (-20 °C). Scheme 7 Figure 1. Molecular structure of 12g (hydrogen atoms have been omitted for clarity). Table 5. Selected Bond Distances (Å) for 12g Cr-C1 Cr-C16 Cr-C17 Cr-C18 Cr-C19 Cr-C20

All attempts to obtain X-ray quality crystal from carbenes 9 were unsuccessful. Therefore, to gain some insight into the structure of these compounds, we prepared the pentacarbonyl derivatives 12 (Scheme 8, Table 4) by reaction of some carbenes Scheme 8

2.140(3) 1.884(5) 1.884(4) 1.891(4) 1.851(5) 1.887(5)

C1-C2 C2-C3 C3-C4 C4-C5 C1-C12 C2-C14 C3-N

1.354(5) 1.493(5) 1.432(5) 1.336(5) 1.485(4) 1.481(4) 1.304(5)

C12-O1 C14-O3 C16-O6 C17-O7 C18-O8 C19-O9 C20-O10

1.204(5) 1.199(4) 1.144(6) 1.146(5) 1.142(5) 1.148(5) 1.137(6)

Table 6. Selected Dihedral Angles (deg) for 12g Cr-C1-C2-C3 C1-C2-C3-C4 C2-C3-C4-C5 N-C3-C4-C5

-5.6.1(5) -81.7(4) -6.5(5) 173.3(4)

Cr-C1-C12-O1 C1-C2-C14-O3 C1-C2-C3-N C14-C2-C3-N

-79.2(4) -1.0(6) 99.2(4) -83.1(4)

Table 7. Crystal Data and Structure Refinement for 12g empirical formula formula weight temperature wavelength crystal system, space group unit cell dimensions

Table 4. Complexes 12 Prepared carbene

R1

NR2

yield (%)

12e 12f 12g

Ph Fu Fu

N(CH2CH2)2O N(CH2CH2)2O NMe2

90 85 95

9 with CO. The structure of complexes 12 was postulated on the base of its 1H and 13C NMR analysis. The most significant spectroscopic finding for 12g is the following. The carbene carbon resonance chemical shift, 224.1 ppm, for 12g is 20 ppm upfield compared with that of its tetracarbonyl analogue 9g, and the chemical shift for the C5-C6 double bond signals (148.4 and 122.8) is now indicative of an uncoordinated double bond. The pentacarbonyl moiety is reflected by the two signals in the metal-carbonyl region. The X-ray structure of 12g (Figure 1, Tables 5-7) reveals some details about the nature of the bond between the chromium and the carbene atom. The complex can be best described as a zwitterion in which the nitrogen-containing conjugated system is positively charged, since the unit Cr-C1-C2-C14 is on a

volume Z, calculated density absorption coefficient F(000) crystal size θ range for data collection index ranges reflections collected/unique completeness to 2θ ) 24.98° refinement method data/restraints/parameters goodness-of-fit on F2 final R indices [I > 2σ(I)] R indices (all data) largest diff. peak and hole

C20H17NO10Cr 483.35 293(2) K 0.710 73 Å triclinic, P1h a ) 9.1582(18) Å; R ) 103.80(2)° b ) 10.905(2) Å; β ) 100.23(2)° c ) 14.564(5) Å; γ ) 105.08 (1)° 1318.6(6) Å3 2, 1.217 Mg/m3 0.590 mm-1 568 0.26 × 0.20 × 0.17 mm 1.49-24.98° 0 e h e 10, -12 e k e 12, -17 e l e 17 4940/4622 [R(int) ) 0.0185] 100.0% full-matrix least-squares on F2 4622/0/331 1.288 R1 ) 0.0429, wR2 ) 0.1102 R1 ) 0.0998, wR2 ) 0.1227 0.530 and -0.522 e Å-3

plane almost perpendicular to that formed by N-C3-C4-C5 (dihedral angle C1-C2-C3-N ) 99.2°).26 This alkyne insertion reaction has opened an easy route for the preparation of different tetra- and pentacarbonyl carbene complexes with an electron acceptor group directly attached to the carbene atom. There are few reports concerning group VI metal carbenes with this structural characteristic. In fact, to the

First Stepwise Do¨ tz Reaction

J. Am. Chem. Soc., Vol. 122, No. 7, 2000 1319

Scheme 9

Scheme 10

Table 8. Cyclopentadienes 13 Prepared compd 13a 13b 13c 13d 13e 13h 13i

R1

R2

CH2CH2CH2 OCH2CH2CH2 CH3 H CH3 CH2OCH3 H Ph H 2-furyl H 2-furyl

R3

R4

CH2CH2OCH2CH2 CH2CH2OCH2CH2 CH2CH2OCH2CH2 CH2CH2OCH2CH2 CH2CH2OCH2CH2 CH3 H H H

yield (%) 74 62 68 65a 52b 44 35

a As a 60:40 mixture of regioisomers. b As a 71:29 mixture of regioisomers.

extent of our knowledge, only two other approaches to this family of carbenes have been reported.27,28 These syntheses have the limitation that, along with the electron attractor group, only an amino group directly attached to the carbene atom can be introduced in the structure of the complex. The reactions reported herein allow the introduction, along with the acceptor group, of a dienyl system with very different possible substituents in R, γ, and δ positions and several amines in position β. Furthermore, various acid derivatives can be introduced as electron attractor moieties, thus expanding the range of functional groups that have been attached to a carbene complex. Even more, as far as we know, this is the first synthesis of a stable chelated dienyl carbene complex of chromium. The structure of complexes 9 differs from that of complexes usually postulated as intermediates in Do¨tz reaction. In fact, complexes 9 are isomers of IV (Scheme 1) in which the metal has migrated from the internal to the terminal double bond in order to be stabilized.29,30 To establish whether carbenes 9 are, in fact, intermediates of Do¨tz reaction, we decided to study the thermal behavior of a representative selection of them. We started with complexes 9 prepared from DMAD insertion, which undergo the cyclopentannulation process to afford carbocycles 13 (Scheme 9, Table 8). Decomposition of carbenes 9a-d takes place at 25 °C while reaction of 9e, 9h, and 9i is more sluggish and it is necessary to warm their THF solutions to 60 °C to bring the reaction to completion in reasonable time. Compounds 13 were obtained in some cases as an inseparable mixture of isomers in which the double bonds are shifted through the ring. To ascertain the identity of the cyclopentadienes, 13c and 13e were hydrolyzed to afford cyclopentenones (26) The nature of the bonding between the metal and the carbene carbon can be seen as intermediate between that of a typical carbene and that of a Csp2-bonded alkyl pentacarbonyl chromate. As a consequence, Cr-carbene and Cr-CO bond distances for 12g, and the Cr-C 13C NMR chemical shift (224 ppm), are intermediate between those of standard Fischer aminovinyl carbene complexes and those reported for β-phosphoniumalkyland R-imoniumalkylpentacarbonylchromates. (a) Aumann, R.; Jasper, B.; La¨ge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (b) Barluenga, J.; Toma´s, M.; Rubio, E.; Lo´pez-Pelegrı´n, J. A.; Garcı´a-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695. (27) Dvora´k, D.; Ludwig, M. Organometallics 1998, 17, 3627. (28) (a) Aumann, R.; Fischer, E. O. Angew. Chem., Int. Ed. Engl. 1967, 6, 879. (b) Aumann, R.; Fischer, E. O. Chem. Ber. 1968, 101, 954. (29) This stabilization has been previously postulated: Harvey, D. F.; Grenzer, E. M.; Gantzel, P. K. J. Am. Chem. Soc. 1994, 116, 6719. (30) We are aware that, although the most stable form of tetracarbonyl dienylcarbene complexes is 9 and not IV, it is this one which should be formed initially from insertion of acetylene, and, if an equilibrium between both isomers occurs, complexes IV might be also the reactive species.

Table 9. Phenols 15 Prepared carbene

phenol

Z

yield (%)

9j 9k 9l

15j 15k 15l

CO2Me CONMe2 CN

92 45 20

14c and 14e as single stereoisomers. The stereochemistry of 14 was postulated by NOE experiments performed on the diethyl derivative 14e′, since the signal for one of the hydrogens of the cycle in 14e is obscured by those of the ester methoxy groups. The reactions of Fischer aminovinyl carbene complexes and alkynes have been reported to produce phenol derivatives as the major product under thermal conditions,14 and, to the best of our knowledge, there is only one example of cyclopentannulation reaction of Fischer aminovinyl carbenes and alkynes.14a Although quite a large number of pentacarbonyl dienyl carbene complexes are known to give rise to cyclopentadienes,31 as far as we know, no example has been reported previously with chelated tetracarbonyl analogous. A similar treatment was carried out with complexes arising from propiolic acid derivatives, and surprisingly a completely different behavior was found. As is shown in Scheme 10, complexes 9j-l undergo CO insertion prior to cyclization to give phenols 15 in a completely selective fashion, without detectable traces of corresponding cyclopentadiene (Table 9).32 A possible explanation for the selectivity of this reaction will be given in the Discussion. These results show that metallatrienes 9j-l can be considered as real intermediates in the Do¨tz benzannulation process. Although a few examples of complexes similar to the intermediate IV (Scheme 1) have been described,19,33 as far as we know there is no previous report of the thermal conversion of a wellcharacterized η3-dienyl carbene or η3-vinyl carbene into a phenol.34 This conversion has been proposed to occur via a complexed dienylketene VI (Scheme 1)1a or a metallacycloheptadienone,5 or directly.13b,c To discriminate among these options, we monitorized the decomposition of 9j by NMR. The reaction took place smoothly in 9 h at room temperature, but no intermediate was observed. The only observable products were the starting carbene 9j, the phenol 15j, and its (CO)3Cr complex. We cannot conclude anything from this result, except that if the reaction proceeds via any intermediate, it is transformed faster than produced. (31) Aumann, R.; Nienaber, H. AdV. Organomet. Chem. 1997, 41, 163. (32) (CO)3Cr adducts of the hydroxyl free phenol can be obtained with the suitable workup of the reaction, by oxygen-free chromatography or crystallization from the reaction crude material. Nevertheless, better yields are obtained by oxidative cleavage of the chromium-arene bond in mild conditions (air and sunlight) followed by silica gel chromatography to yield the metal-free phenol. (33) (a) Mitsudo, T.; Fujita, K.; Nagano, S.; Suzuki, T.; Watanabe, Y.; Masuda, H. Organometallics 1995, 14, 4228. (b) Park, J.; Kim, J. Organometallics 1995, 14, 4341. (34) The thermal cyclization of an η1-dienylcarbene to a phenol has been observed: Barluenga, J.; Aznar, F.; Palomero, M. A.; Barluenga, S. Org. Lett. 1999, 1, 541.

1320 J. Am. Chem. Soc., Vol. 122, No. 7, 2000

Barluenga et al.

Scheme 11

Table 10. Phenols 16 Prepared carbene

R1

phenol

yield (%)

9e 9j

CO2Me H

16e 16j

71 32

On the other hand, it is well known that acceptor-substituted carbene complexes of late transition metals have been proposed for a long time as very unstable intermediates in the reaction of organic ylides with electrophilic coordinatively unsaturated late transition metals.35 Therefore, as we have mentioned before, it is reasonable to think that the high stability of complexes 9 has to be ascribed to the electron donor effect of the amine. We envisioned that it could be interesting to try to modify the nature of the metallatriene complex by exchanging the amine group for another without electron-donating ability, such as an alkyl group. Thus, complexes 9e and 9j were treated with methyllithium at -80 °C to give phenols 16 (Scheme 11, Table 10) almost instantaneously. This result can be rationalized by an initial attack of the methyllithium at the β position, followed by amine extrusion, which furnishes the nonstabilized carbene 17. This carbene lacks the stabilization of the amine and undergoes cyclization quickly at low temperature to afford the phenol 16 in a fashion similar to the last steps of Do¨tz reaction (see Discussion). As a whole, this reaction can be seen as the equivalent of a Do¨tz reaction with a nonstabilized vinyl carbene complex. Discussion It is generally accepted that the first and rate-determining step of Do¨tz reactions is the thermal decarbonylation of the starting pentacarbonyl carbene I to yield the tetracarbonyl carbene complex II, which is coordinatively unsaturated (Scheme 12). This intermediate can be stabilized by intramolecular coordination of the double bond,36 leading to a η3-allylidene complex II′. From the NMR data of isolated carbenes of the type II′ (complexes 5a-e) it is reasonable to conclude that there is an equilibrium between species II and II′ in solution, which is fast but more attracted to the more stable chelate form, although it has never been observed.37 This mode of stabilization can be achieved with reasonable ease by alkenyl carbene complexes, but not by aryl ones, since it implies an η2coordination. It is at this early stage where the pathways of reactions of alkenyl and aryl complexes first differ. (35) Do¨rwald, F. Z. Metal Carbenes in Organic Synthesis; Wiley-VCH: Weinheim, 1999. (36) Theoretical calculations show that this coordination is stabilizing.11 (37) This kind of equilibrium might occur not only with aminoalkenyl carbenes but also with alkoxyalkenyl carbenes.11

The next step would consist of the coordination of the acetylene to yield complex III, followed by insertion in the metal-carbene bond giving rise to a new η3-allylidene complex IV, in which the newly formed double bond can be Z or E, depending on the stereochemistry of the process. Theoretical calculations concerning this step conclude that this insertion is an exothermic process with a very low energetic barrier, if any at all. Wulff and colleagues have proposed recently that it is at this stage where the partitioning between cyclopentadienes VIII and phenols IX, on one side, and furans and bicyclic lactones, on the other side, occurs.2a They stated that the product distribution is determined by the equilibrium between both isomers of η3-allylidene, which can interchange in the reaction conditions. In the work described herein, only products arising from the E isomer of complexes IV have been observed, but, since the insertion process takes place at low temperature, we cannot conclude whether this is the kinetic product or the only one possible from the starting materials. Species of type IV-E arising from alkenyl carbene complexes can be stabilized by isomerization to the 1,4,5-η3-pentadienylidene form XI. This stabilization occurs by releasing the strain of the small chelation ring and also by liberating the internal double bond that allows the conjugation of the lone pairs of the heteroatom with the carbene moiety.38 It is important to notice that this kind of complexation might not be favorable in intermediates arising from aryl carbenes, as an η2-coordination of the aryl moiety should be necessary. Assuming that the energetic barrier between III and IV is almost null,12 the one between IV and XI must be at least lower than the barrier of alkyne coordination to the metal, since experiments monitored by NMR spectroscopy did not show accumulation of IV in the reaction mixture. Only a smooth conversion of the signals of complex 5a in the signals of complex 9a could be observed upon addition of DMAD at low temperature. Although an X-ray structure of none of the complexes 9 could not be obtained, we propose the structure XI depicted in Scheme 12 according to the MNR data. In this structure there is a very important donation from the nitrogen lone pairs to the chromium atom.39 The terminal double bond must adopt a planar disposition toward the chromium atom in order to chelate the metal efficiently. This disposition cannot be achieved without a significant twisting of the metallatriene unit, which is no longer conjugated. This folding occurs around the C3-C4 single bond between the terminal double bond and the rest of the π system, which would be on a plane. This disposition is essentially the same as that which has been obtained by DFT calculations on a similar system.13c A slightly different structure can be proposed for those carbenes XI, where R1 is an ester group. In this case, the negative charge supported by the metal in the zwitterionic form can be stabilized by retrodonation to the ester group, and conjugation between the chromium and the imonium moiety is no longer necessary. Now, a conjugation is possible between the imonium and the terminal double bond maintaining the chelation stabilization. This can happen assuming a rotation around the bond between C2 and C3 instead of that between C3 and C4. This structure is depicted in Scheme 12 as XI′. The strength of the coordination of the double bond to the metal is now increased since (a) the structural arrangement is geometrically more accurate and (b) the double bond is more (38) This stabilization has been calculated to be 23 kcal/mol for tetracarbonyl(3-hydroxypenta-2,4-dienylidene)chromium(0).13c (39) This effect would explain the unexpected value for the 13C chemical shift of the carbene carbon in these species (e.g., 246 ppm for 9a).

First Stepwise Do¨ tz Reaction

J. Am. Chem. Soc., Vol. 122, No. 7, 2000 1321

Scheme 12

electron deficient, thus leading to a greater contribution of d-π* back-bonding. This structure has been proposed since it is essentially the same as that which has been observed in the X-ray structure of the related pentacarbonyl complex 12g, except for the complexation of the terminal double bond. In this structure, we reproduce the zwitterionic character, the conjugation of the chromium with the ester instead of the imonium moiety, and the conjugation of this imonium with the double bond. From the greater thermal stability of the complexes bearing an ester in position 2, as compared to those that lack it (9e compared with 9j) we can conclude that the overall effect is stabilizing. By assuming these different structures for XI and XI′, the different outcome of the thermal progress of both structures can be rationalized as follows: in the latter (XI′), an intramolecular nucleophilic attack from the negatively charged chromium on the vinyl imonium moiety could be more advantageous.40,41 This attack yields the metallacyclohexadiene V which would undergo reductive elimination to furnish the five-membered ring product VIII exclusively. On the other hand, the conformer XI is less likely to suffer this kind of attack, since the double bond is not conjugated with the imonium cation. Thermal evolution of these intermediates would involve a CO insertion process giving rise to phenol IX, which is the main product of the Do¨tz reaction of alkenyl amino carbenes. (40) A similar attack has been proposed for the [4 + 1] reaction of chromium phenylmethoxycarbene with 2-methyl-1,3-dimorpholino-1,3butadiene. Barluenga, J.; Aznar, F.; Ferna´ndez, M. Chem. Eur. J. 1997, 3, 1629. (41) The formation of VIII from XI′ could also take place through a Nazarov-type reaction. Yamashita, A. Tetrahedron Lett. 1986, 27, 5915.

It is worth noting that the allochemical effect proposed by Wulff and colleagues as necessary for the CO insertion to take place in aryl carbene complexes reactions2e cannot be claimed in this case since the cyclization step is carried out starting from isolated carbenes XI, in the absence of additional alkyne. It is known that the reactions of alkenyl carbene complexes are little or not affected by changes in the concentration of alkyne.2d This lack of influence can be explained by a mechanism in which CO insertion is concomitant with the complexation of the Cr(CO)3 moiety to all three double bonds of the dienylketene VI just formed. The chromium maintains an 18-electron configuration throughout all the CO insertion process.42 The evolution of this dienylketene through the usually proposed electrocyclic closure leads to Cr(CO)3-complexed cyclohexadienone VII and then to the complexed phenol IX. Finally, the electronic nature of the differentiation between pathways leading to five- and six-membered ring products can be supported by the reaction of complexes XI (and XI′) with carbon nucleophiles. This reaction gives phenols in which the amine group has been substituted for the nucleophile. In the proposed mechanism for this reaction, we assume that this substitution takes place as the first step, by nucleophilic attack on the imonium cation of XI, followed by amine extrusion, leading to formation of metallatriene XII. This complex is very similar to XI except for the fact that no stabilization can be achieved by electron donation toward the metal. Charge separation is not produced, and a nucleophilic attack of the (42) An alternative mechanism that accounts for the direct formation of VII from XI without the intervention of an additional molecule of alkyne in reactions of alkenyl carbenes has been proposed.13c

1322 J. Am. Chem. Soc., Vol. 122, No. 7, 2000 chromium to the complexed double bond is not favorable. The most favorable reaction pathway would be the insertion of CO that leads, following a mechanism analogous to the one explained above, to the final product, the phenol XIV, as a (CO)3Cr complex. This reaction is very fast even at low temperature, suggesting that the CO insertion process has a low energetic barrier as well. Conclusions We report herein a comprehensive study of the thermal and photochemical decarbonylation of alkenyl amino carbene complexes. This reaction is quite general and furnishes a new type of carbenes 5 that are valuable as low-temperature generators of 16-electron tetracarbonyl chromium carbene complexes. The synthesis and isolation of these complexes have allowed us to carry out the reaction with alkynes at low temperature and to isolate and characterize the carbene complexes 9. Since some of these carbene complexes lead to phenols upon warming, both complexes 5 and 9 can be considered as Do¨tz benzannulation reaction intermediates. The overall process can be seen as a Do¨tz reaction carried out in three separate steps at low temperature. As far as we know, this is the first example of such a stepwise Do¨tz reaction. On the other hand, the insertion of alkynes into complexes 5 can be considered as a general method for the synthesis of electron-withdrawing substituted carbene complexes, either as η1-pentacarbonyl or as η3tetracarbonyl. As far as we know, this is the first synthesis of such a chelated dienyl carbene complex. The reaction of complexes 5 with DMAD is also the first general reaction of cyclopentannulation of alkenylcarbene complexes with alkynes. Finally, we have carried out a three-component Do¨tz reaction in which we have substituted the carbene donor group for a carbonated nucleophile. Experimental Section All reactions were carried out under nitrogen atmosphere. Tetrahydrofuran (THF), toluene, and ether were dried by distillation from sodium/benzophenone. Melting points are uncorrected. Chromatographic purifications were performed on silica gel (230-400 mesh) by flash technique. Analytical TLC plates (covered with silica gel 60 F254) were viewed by UV light or developed by heating after treatment with an acidic solution of Ce(IV) and Mo(VI). 1H and 13C NMR spectra were recorded on a Bruker AC-200 or AC-300 spectrometer. Chemical shifts refer to TMS in 1H experiments and to deuterated solvent in 13C experiments. IR analyses were performed on a Mattson 3000 FTIR spectrometer. HRMS spectra were recorded on a Finnigan-Mat 95. Elemental analyses were obtained on a Perkin-Elmer 240-B analyzer. Photochemical reactions were carried out in Schlenk tubes (Pyrex) equipped with external jackets for continuos coolant flow (2-propanol) and placed 2 cm away from a 400-W medium-pressure mercury lamp. The solutions were deoxygenated by nitrogen bubbling for 15 min prior to irradiation. In the cases in which a loss of CO is expected, bubbling was maintained during irradiation. The reactions were monitored by TLC or IR techniques until disappearance of the starting materials. General Procedure for the Preparation of η3-Aminovinyl Carbene Complexes 5. A 0.05 M solution of aminovinyl carbene complex 1 in degassed THF was irradiated at temperatures between -45 and -35 °C. The reaction was monitored by IR analyses until disappearance of the absortion signals corresponding to the starting complex. For complexes 5a-d, the solution was then filtered through a pad of Celite, and the solvents were evaporated under vacuum. The residue was crystallized in deoxygenated hexane-dichloromethane. Complexes 5e-g were not isolated but were used in situ in the next reaction. Tetracarbonyl[η 3 -(1-cyclopentenyl)morpholinomethylene]chromium(0) (5a). A 0.71 g (2 mmol) amount of 1a was irradiated for 4 h to yield, after crystallization, 0.62 g (1.86 mmol, 94%) of 5a. Mp: 137-139 °C (red prisms). Rf ) 0.19 (hexane:ethyl acetate 3:1).

Barluenga et al. NMR (300 MHz, CDCl3): δ ) 4.67 (t, 1H, J ) 3.3 Hz, dCH), 4.01-3.63 (m, 8H, N(CH2CH2)2O), 2.67-2.51 (m, 1H), 2.35-2.20 (m, 2H), 1.96 (dd, 1H, J ) 7.8, 14.0 Hz), 1.88-1.71 (m, 1H), 1.64-1.35 (m, 1H). 13C NMR (75.5 MHz, -40 °C, CD2Cl2): δ ) 257.6 (CdCr), 235.8 (CO), 234.9 (CO), 224.2 (CO), 222.0 (CO), 86.6 (dC), 85.0 (dCH), 67.5 (NCH2CH2O), 67.1 (NCH2CH2O), 58.5 (NCH2CH2O), 57.0 (NCH2CH2O), 35.4 (dCCH2), 31.1 (CH2CH2CH2), 20.5 (CH2CH2CH2). Anal. Calcd for C14H15NO5Cr: C, 54.36; H, 4.85; N, 4.53. Found: C, 54.58; H, 4.64; N, 4.25. Tetracarbonyl(η3-1-morpholino-3-phenyl-2-propenylidene)chromium(0) (5e). A solution of 20 mg of 1e in 1 mL of CD2Cl2 was irradiated in a NMR tube under static vacuum for 6 h. Each hour, the sample was degassed (two freeze-pump-thaw cycles) in order to remove the released CO. 1H and 13C NMR analyses showed a 40:60 mixture of 1e and another compound that was identified as 5e. 1H NMR (300 MHz, CD2Cl2): δ ) 7.50-7.20 (m, 5H, Ph), 5.01 (d, 1H, J ) 12 Hz, dCH), 4.93 (d, 1H, J ) 12 Hz, dCH), 4.00-3.60 (m, 8H, N(CH2CH2)2O). 13C NMR (75.5 MHz, CD2Cl2): δ ) 257.8 (CdCr), 229.6 (broad, 4×CO), 138.3 (C ipso), 129.3 (2×CH, Ph), 127.9 (CH, p-Ph), 127.6 (2×CH, Ph), 75.0 (dCH), 68.1 (NCH2CH2O), 67.8 (NCH2CH2O), 64.9 (dCH), 61.2 (NCH2CH2O), 57.8 (NCH2CH2O). Reaction of Carbene Complex 1a with Phenylacetylene. A solution of 0.18 g (0.5 mmol) of 1a and 0.10 g (1 mmol) of phenylacetylene in 10 mL of THF was refluxed for 1 h. The solvents were removed under reduced pressure, and the residue was chromatographed using hexane:ethyl acetate 1:1 as eluent. Two products were obtained: 0.08 g (0.20 mmol, 40%) of tricarbonyl (η5-1,4,5,6tetrahydro-1-morpholino-3-phenylpentalene)chromium(0) (6) and 0.09 g (0.21 mmol, 42%) of tricarbonyl (η6-2,3-dihydro-4-hydroxy-7morpholino-5-phenylindene)chromium(0) (7). Spectral data for 6. Rf ) 0.33 (hexane:ethyl acetate 3:1). 1H NMR (300 MHz, CDCl3): δ ) 7.50-6.91 (m, 5H, Ph), 5.69-5.40 (m, 2H), 3.80-3.55 (m, 4H, N(CH2CH2)2O), 3.00-1.40 (m, 10H, N(CH2CH2)2O, CH2-CH2-CH2). 13C NMR (75.5 MHz, CDCl ): δ ) 238.9 (3×CO), 133.6 (C, aryl), 3 128.3 (2×CH, Ph), 127.5 (CH, p-Ph), 126.7 (2×CH, Ph), 106.1 (dC), 102.5 (dC), 100.3 (dCH), 87.7 (dC), 84.0 (CH), 66.1 (N(CH2CH2)2O), 50.1 (N(CH2CH2)2O), 25.6 (CH2), 24.2 (CH2), 22.2 (CH2). Anal. Calcd for C21H21NO4Cr: C, 62.53; H, 5.25; N, 3.47. Found: C, 62.81; H, 5.52; N, 3.67. Spectral data for 7: Rf ) 0.14 (hexane:ethyl acetate 3:1). 1H NMR (300 MHz, THF-d8): δ ) 7.55-7.05 (m, 5H, Ph), 5.37 (s, 1H, aryl), 3.70-3.30 (m, 4H, N(CH2CH2)2O), 3.00-2.50 (m, 4H, N(CH2CH2)2O), 2.20-1.80 (m, 2H, CH2-CH2-CH2), 1.75-1.45 (m, 4H, CH2-CH2-CH2). 13C NMR (75.5 MHz, THF-d8): δ ) 237.2 (3×CO), 137.5 (C, aryl), 131.6 (2×CH, Ph), 130.3 (CH, p-Ph), 130.2 (2×CH, Ph), 123.7 (C, aryl), 120.3 (C, aryl), 115.7 (C, aryl), 104.9 (C, aryl), 100.9 (C, aryl), 90.0 (CH, aryl), 68.9 (N(CH2CH2)2O), 54.2 (N(CH2CH2)2O), 33.2 (CH2), 31.8 (CH2), 27.7 (CH2). Anal. Calcd for C22H21NO5Cr: C, 61.25; H, 4.91; N, 3.25. Found: C, 61.47; H, 5.21; N, 3.48. Reaction of Carbene Complex 5a with Phenylacetylene. A solution of 0.17 g (0.5 mmol) of 5a in 20 mL of CH2Cl2 was treated with 0.10 g (1 mmol) of phenylacetylene at room temperature. The reaction was monitored by TLC. When the starting material was consumed (6 h) the solvents were removed under reduced pressure, and the residue was chromatographed to yield 0.08 g (0.23 mmol, 46%) of 1a as the only identifiable product. When this reaction was carried out in refluxing THF temperature, the disappearance of the carbene took 1 h, and the products isolated after column chromatography were 6 (0.04 g, 0.1 mmol, 20%) and 7 (0.04 g, 0.1 mmol, 20%). General Procedure for the Preparation of 1,4,5-η3-Methoxycarbonyldienylcarbene Complexes 9. A 0.1 M solution of carbenes 5a-d in CH2Cl2 was treated with 1 equiv of DMAD at -20 °C for 24 h, and then a 2-fold volume of hexane was added. The reaction was cooled to -40 °C, and a dark brownish solid precipitated after 1 day. The solution was decanted under N2 at -20 °C and the resultant solid washed with hexane to give 9a-d. These solids are thermally unstable, and satisfactory elemental analyses could not been obtained in one case. Complexes 9e-g and 9j-l were prepared by irradiation of a 0.05 M solution of aminovinyl carbene complex 1e-g in degassed THF at temperatures between -45 and -35 °C. The reaction was monitored by IR analyses until disappearance of the absortion signals correspond1H

First Stepwise Do¨ tz Reaction ing to the starting complex. DMAD (1 equiv) was added at -40 °C, and the reaction was warmed and allowed to react overnight. Complexes 9h-i were prepared by irradiation of solutions of 1h-i in the presence of DMAD in THF. In both cases, the solutions were evaporated under vacuum, and the residue was chromatographed using hexane:ethyl acetate 1:1 as eluent. Tetracarbonyl[1,4,5-η3-(1-cyclopentenyl)-1,2-dimethoxycarbonyl3-morpholinopropenylidene]chromium(0) (9a). 5a (0.33 g, 1.0 mmol) was reacted with 0.14 g (1.0 mmol) of DMAD in 10 mL of CH2Cl2 to afford 0.25 g (0.54 mmol, 54%) of 9a as a brown powder. Rf ) 0.11 (hexane:ethyl acetate 1:1). 1H NMR (300 MHz, CD2Cl2): δ ) 4.81 (s, 1H, CdCH), 3.90 (s, 3H, CO2CH3), 3.72-4.20 (m, 8H, N(CH2CH2)2O), 3.66 (s, 3H, CO2CH3), 2.36-2.92 (m, 4H, CH2CH2CH2), 1.61-1.94 (m, 2H, CH2CH2CH2), 13C NMR (50.3 MHz, CDCl3): δ ) 245.9 (Cd Cr), 231.1 (CO), 230.0 (CO), 220.9 (CO), 220.2 (CO), 178.1 (CO2CH3), 167.5 (CO2CH3), 157.9 (dC), 130.7 (dC), 102.1 (dC), 93.8 (dCH),), 67.1 (NCH2CH2O), 66.8 (NCH2CH2O), 54.2 (NCH2CH2O), 53.8 (NCH2CH2O), 52.3 (CO2CH3), 51.4 (CO2CH3), 36.7 (CH2Cd), 34.0 (CH2Cd), 20.7 (CH2CH2CH2). Anal. Calcd for C20H21NO9Cr: C, 50.96; H, 4.49; N, 2.97. Found: C, 50.80; H, 4.37; N, 2.63. Tetracarbonyl(1,4,5-η3-1,2-dimethoxycarbonyl-3-morpholino-5phenyl-2,4-pentadien-1-ylidene)chromium(0) (9e). 1e (1.00 g, 2.5 mmol) was irradiated in 150 mL of degassed THF at -40 °C until IR analysis showed no absortion signals of the starting carbene. Then, 0.36 g (2.5 mmol) of DMAD was added, and the reaction mixture was allowed to react overnight to afford, after chromatography, 0.75 g (1.4 mmol, 55%) of 9e. Mp: 139-141 (dark green prisms). Rf ) 0.14 (hexane:ethyl acetate 1:1). 1H NMR (200 MHz, CDCl3): δ ) 7.597.07 (m, 5H, Ph), 4.86 (d, 1H, J ) 11.5 Hz, dCH), 4.73 (d, 1H, J ) 11.5 Hz, dCH), 4.51-3.90 (m, 8H, N(CH2CH2)2O), 3.82 (s, 3H, CO2CH3), 3.65 (s, 3H, CO2CH3). 13C NMR (50.3 MHz, CDCl3): δ ) 252.5 (CdCr), 235.0 (CO), 228.8 (CO), 226.7 (CO), 222.9 (CO), 178.1 (CO2CH3), 177.3 (CO2CH3), 157.6 (dC), 138.3 (C ipso), 128.5 (2×CH, Ph), 128.2 (CH, p-Ph), 126.2 (2×CH, Ph), 122.68 (dC), 89.8 (dCH), 68.2 (dCH), 66.4 (2×NCH2CH2O), 53.9 (NCH2CH2O), 51.8 (CO2CH3), 51.4 (NCH2CH2O), 50.9 (CO2CH3). Anal. Calcd for C23H21NO9Cr: C, 54.44; H, 4.17; N, 2.76. Found: C, 54.43; H, 4.22; N, 2.78. Tetracarbonyl(1,4,5-η3-5-furyl-1,2-dimethoxycarbonyl-3-methylamino-2,4-pentadien-1-ylidene)chromium(0) (9h). 1h (0.65 g, 2.0 mmol) and DMAD (0.28 g, 2 mmol) were irradiated in 150 mL of deoxygenated Et2O at -40 °C for 6 h. The reaction crude material was chromatographed to afford 0.09 g of 9h (0.2 mmol, 10%) and 0.04 g of 13h (0.2 mmol, 10%). In addition, 0.36 g (1.1 mmol, 55%) of 1h was recovered unreacted. Longer reaction time did not increase the chemical yield of 9h. Mp: 147-150 °C. Rf ) 0.52 (dichloromethane:ethyl acetate 8:1). 1H NMR (300 MHz, CDCl3): δ ) 10.74 (br s, 1H, NH), 7.23 (s, 1H, 5-Fu), 6.39 (d, 1H, J ) 3.4 Hz, 4-Fu), 6.32 (d, 1H, J ) 1.5 Hz, 3-Fu), 4.93 (d, 1H, J ) 10.5 Hz, dCH), 4.78 (d, 1H, J ) 10.5 Hz, dCH), 3.78 (s, 3H, CO2CH3), 3.64 (s, 3H, CO2CH3), 3.57 (d, 3H, J ) 4.8 Hz, NCH3). 13C NMR (75.5 MHz, CDCl3): δ ) 271.3 (CdCr), 234.5 (CO), 227.0 (CO), 226.2 (CO), 223.3 (CO), 186.9 (CO2CH3), 177.3 (CO2CH3), 161.1 (dC), 153.7 (C, 2-Fu), 141.8 (CH, 5-Fu), 123.3 (dC), 111.9 (CH, 4-Fu), 107.4 (CH, 3-Fu), 77.4 (dCH), 63.5 (dCH), 52.0 (CO2CH3), 50.9 (CO2CH3), 32.4 (NCH3). Anal. Calcd for C18H15NO9Cr: C, 48.99; H, 3.43; N, 3.17. Found: C, 49.18; H, 3.63; N, 3.28. General Procedure for the Preparation of η1-Methoxycarbonyldienylcarbene Complexes 12e-g. A 0.1 M solution of carbene complexes 9e-g was pressurized under 4 bar of CO for 2 days. The solvent was then evaporated under vacuum and the crude mixture chromatographed (silica gel, hexane:ethyl acetate 1:1). Pentacarbonyl[3-(dimethylamino)-5-furyl-1,2-dimethoxycarbonyl-2,4-pentadien-1-ylidene]chromium(0) (12 g). Reaction of 0.10 g (0.22 mmol) of 9g afforded 0.10 g (0.21 mmol, 95%) of 12g. Mp: 128-130 °C (black prisms). Rf ) 0.05 (hexane:ethyl acetate 1:1). 1H NMR (300 MHz, CDCl3): δ ) 7.67 (s, 1H, 5-Fu), 7.60 (d, 1H, J ) 15 Hz, dCH), 7.09 (d, 1H, J ) 15 Hz, dCH), 6.96 (s, 1H, 4-Fu), 6.59 (s, 1H, 3-Fu), 3.83 (s, 3H, CO2CH3), 3.67 (s, 3H, CO2CH3), 3.61 (s, 6H, N(CH3)2). 13C NMR (75.5 MHz, CDCl3): δ ) 224.1 (CdCr), 219.8 (CO trans), 218.4 (4×CO cis), 179.1 (CO2CH3), 178.0 (CO2CH3), 157.7 (dC), 150.5 (C, 2-Fu), 148.4 (dCH), 141.4 (CH, 5-Fu), 124.2 (dC),

J. Am. Chem. Soc., Vol. 122, No. 7, 2000 1323 122.8 (dCH), 114.6 (CH, 3-Fu), 114.1 (CH, 4-Fu), 51.9 (CO2CH3), 50.4 (CO2CH3), 44.9 (NCH3), 41.8 (NCH3). Anal. Calcd for C20H17NO10Cr: C, 49.70; H, 3.54; N, 2.90. Found: C, 49.71; H, 3.64; N, 2.95. Crystallographic Structural Determination. Data collection, crystal, and refinement parameters for 12g are collected in Table 7. The unit cell parameters were obtained from the least-squares fit of 25 reflections. On all reflections, profile analysis was performed.43 Lorentz and polarization corrections were applied, and the data were reduced to F2 values using THE REFLEX.44 The structures were solved by Patterson methods using the program DIRDIF.45 Refinement on F2 was done using SHELXL 97.46 Non-hydrogen atoms were refined anisotropically. Hydrogen atoms were calculated geometrically through HFIX and refined riding with common isotropic thermal parameters. Atomic scattering factors were taken from International Tables for X-Ray Crystallography.47 Geometrical calculations were made with PARST. All calculations were made at the University of Oviedo on the Scientific Computer Center and X-Ray Group DEC/AXP Computers. 1-(1,4,5,6-Tetrahydro-2,3-dimethoxycarbonyl-1-pentalenyl)morpholine (13a). A solution of 0.42 g (0.89 mmol) of 13a in 10 mL of CH2Cl2 was allowed to stand at room temperature for 8 h. The reaction mixture was concentrated and the crude material chromatographed to yield 0.20 g (0.66 mmol, 74%) of 13a as a yellow oil. Rf ) 0.40 (hexane:ethyl acetate 1:1). 1H NMR (300 MHz, CDCl3): δ ) 4.56 (s, 1H, NCH), 3.76-3.54 (m, 4H, N(CH2CH2)2O), 3.65 (s, 3H, CO2CH3), 3.61 (s, 3H, CO2CH3), 3.38-3.13 (m, 4H, N(CH2CH2)2O), 2.69-2.45 (m, 4H, CH2CH2CH2), 2.29-2.02 (m, 2H, CH2CH2CH2). 13C NMR (75.5 MHz, CDCl3): δ ) 175.4 (CO2Me), 170.4 (CO2Me), 164.0 (d C), 149.9 (dC), 123.6 (dC), 108.6 (dC), 66.4 (N(CH2CH2)2O), 60.5 (CH), 52.4 (CO2CH3), 50.6 (CO2CH3), 49.2 (N(CH2CH2)2O), 29.8 (CH2), 27.7 (CH2), 26.5 (CH2). Anal. Calcd for C16H21NO5: C, 62.53; H, 6.89; N, 4.56. Found: C, 62.60; H, 6.99; N, 4.61. Methyl 2-Hydroxy-5-morpholino-3-phenylbenzoate (15j). 9j (0.45 g, 1 mmol) was dissolved in 20 mL of THF and allowed to stand at room temperature for 9 h and then exposed to air and sunlight for several hours to afford, after chromatography, 0.29 g (0.92 mmol, 92%) of 15j. Rf ) 0.35 (hexane:ethyl acetate 1:1). 1H NMR (200 MHz, CDCl3): δ ) 10.92 (s, 1H, OH), 7.64-7.35 (m, 6H, aryl), 7.23 (d, 1H, J ) 3.2 Hz, aryl), 3.98 (s, 3H, CO2CH3), 3.89 (t, 4H, J ) 4.6 Hz, N(CH2CH2)2O), 3.11 (t, 4H, J ) 4.6 Hz, N(CH2CH2)2O). 13C NMR (50.3 MHz, CDCl3): δ ) 170.8 (CO2CH3), 153.5 (C, aryl), 143.7 (C, aryl), 137.3 (C, aryl), 131.1 (C ipso), 129.2 (2×CH, Ph), 128.1 (2×CH, Ph), 127.4 (CH, p-Ph), 127.1 (CH, aryl), 115.5 (CH, aryl), 112.3 (C, aryl), 66.9 (N(CH2CH2)2O), 52.4 (CO2CH3), 50.7 (N(CH2CH2)2O). Anal. Calcd for C18H19NO4: C, 68.99; H, 6.11; N, 4.47. Found: C, 69.21; H, 6.25; N, 4.62. Chromium tricarbonyl-complexed methyl 2-hydroxy5-morpholino-3-phenylbenzoate 15j‚(CO)3Cr is obtained in lower yields by chromatography without exposition to sunlight. In these conditions, 0.36 g (0.80 mmol, 80%) of 15j‚(CO)3Cr (red prisms) was obtained. Mp: 152-154 °C. Rf ) 0.42 (hexane:ethyl acetate 1:1). 1H NMR (300 MHz, CDCl3): δ ) 10.59 (s, 1H, OH), 7.65-7.60 (m, 2H, Ph), 7.45-7.35 (m, 3H, Ph), 5.82 (d, 1H, J ) 2.0 Hz, aryl), 5.78 (d, 1H, J ) 2.0 Hz, aryl), 4.00 (s, 3H, OCH3), 3.83 (m, 4H, N(CH2CH2)2O), 2.92 (m, 4H, N(CH2CH2)2O). 13C NMR (75.5 MHz, CDCl3): δ ) 232.8 (3×CO), 171.5 (CO2CH3), 140.0 (C, aryl), 133.7 (C, aryl), 130.2 (2×CH, Ph), 128.6 (CH, p-Ph), 128.3 (2×CH, Ph), 120.0 (C, aryl), 97.3 (C, aryl), 86.9 (CH, aryl), 78.8 (CH, aryl), 70.8 (C, aryl), 66.0 (N(CH2CH2)2O), 53.4 (CO2CH3), 48.9 (N(CH2CH2)2O). Anal. Calcd (43) (a) Grant, D. F.; Gabe, E. J. J. Appl. Crystallogr. 1978, 11, 114. (b) Lehman, M. S.; Larsen, F. K. Acta Crystallogr. 1974, A30, 580. (44) Gutie´rrez-Rodrı´guez, A.; Aguirre-Pe´rez, A.; Garcı´a-Granda, S. THE REFLEX V 1.2 E 2 Manual del usuario; Departamento de Quı´mica Fı´sica y Analı´tica, Universidad de Oviedo, 19XX. (45) Garcı´a-Granda, S.; Gould, R. O.; Smits, J. M. M.; Smukalla, C.; Beurkens, P. T.; Admiraall, G.; Beurskens, G.; Bosman, W. P. DIRDIF user’s guide Technical report; Crystallography Laboratory: University of Nijmegen, The Netherlands, 19XX. (46) Sheldrick, G. M. SHELXS-97; University of Go¨ttingen, Germany, 19XX. (47) International Tables for X-Ray Crystallography; Birmingham Kynoch Press: Birmingham, UK, 1974 (present distributor, Kluwer Academic Publishers: Dordrecht); Vol. IV.

1324 J. Am. Chem. Soc., Vol. 122, No. 7, 2000 for C21H19NO7Cr: C, 56.13; H, 4.26; N, 3.12. Found: C, 56.35; H, 4.10; N, 2.96. Dimethyl 3-Hydroxy-6-methyl-4-phenylphthalate (16e). A solution of 1 mmol of methyllithium in 10 mL of diethyl ether was added dropwise to a solution of 0.51 g (1 mmol) of 9e in 20 mL of THF at -78 °C. The reaction mixture was then warmed to -60 °C, and a mixture of 3 mL of saturated aqueous NH4Cl and 10 mL of THF was added at this temperature. The reaction mixture was exposed to air and sunlight for several hours. Et2O (20 mL) was added, and the mixture was washed with 0.1 N HCl (2 × 20 mL) and brine (20 mL), dried over Na2SO4, and filtrated through Celite. The volatiles were removed in vacuo, and the residue was chromatographed to furnish 0.21 g (0.71 mmol, 71%) of 16e. Rf ) 0.11 (hexane:ethyl acetate 3:1). 1H NMR (200 MHz, CDCl3): δ ) 11.31 (s, 1H, OH), 7.62-7.40 (m, 5H, Ph), 7.38 (s, 1H, aryl), 3.97 (s, 3H, CO2CH3), 3.94 (s, 3H, CO2CH3), 2.30 (s, 3H, CH3). 13C NMR (50.3 MHz, CDCl3): δ ) 169.7 (CO2CH3), 169.3 (CO2CH3), 157.0 (C, aryl), 138.0 (CH, aryl), 136.4 (C, aryl), 133.6 (C, aryl), 131.6 (C, aryl), 129.2 (2×CH, Ph), 128.1 (2×CH, Ph), 127.6 (CH, Ph), 125.4 (C, aryl), 109.1 (C, aryl), 53.0 (CO2CH3), 52.3 (CO2CH3), 18.4 (CH3). Anal. Calcd for C17H16O5: C, 67.99; H, 5.37. Found: C, 68.34; H, 5.58. In a separate run, chromium tricarbonylcomplexed dimethyl 3-hydroxy-6-methyl-4-phenylphthalate 16e‚Cr(CO)3 was obtained in lower yields by the same aqueous workup and chromatography without exposition to sunlight. In these conditions,

Barluenga et al. 0.25 g (0.57 mmol, 57%) of 16e‚Cr(CO)3 (red prisms) was obtained. Rf ) 0.48 (hexane:ethyl acetate 1:1). 1H NMR (200 MHz, CDCl3): δ ) 10.91 (s, 1H, OH), 7.65-7.55 (m, 2H, Ph), 7.50-7.40 (m, 3H, Ph), 5.94 (s, 1H, aryl), 4.03 (s, 3H, CO2CH3), 3.99 (s, 3H, CO2CH3), 2.15 (s, 3H, CH3). 13C NMR (50.3 MHz, CDCl3): δ ) 230.4 (3×CO), 170.7 (CO2CH3), 166.3 (CO2CH3), 140.4 (C, aryl), 132.8 (C, aryl), 130.1 (2×CH, Ph), 128.7 (CH, Ph), 128.2 (2×CH, Ph), 105.9 (C aryl), 98.4 (CH, aryl), 98.0 (C, aryl), 96.5 (C, aryl), 68.6 (C, aryl), 53.8 (CO2CH3), 53.4 (CO2CH3), 17.8 (CH3). Anal. Calcd for C20H16O8Cr: C, 55.05; H, 3.70. Found: C, 54.91; H, 3.59.

Acknowledgment. This research was supported by the DGICYT (Grant PB97-1271). Supporting Information Available: Experimental procedures and analytical data for all new compounds and X-ray crystallographic data for 12g, including tables of atomic coordinates, bond lengths, bond angles, and anisotropic displacement coefficients (PDF). An X-ray crystallographic file, in CIF format, is also available. This material is available free of charge via the Internet at http://pubs.acs.org. JA991865J